Hydrolysis resistant and biodegradable aliphatic-aromatic copolyester resin composition

Abstract

The present invention relates to an aliphatic-aromatic copolyester resin composition with excellent hydrolysis resistance, wherein an unsaturated compound or an anhydride thereof is introduced into a molecular structure, and specifically, the aliphatic-aromatic copolyester resin composition can be manufactured into all molded products by extrusion, injection and the like, by solving problems with respect to physical properties, processability, reaction rates and water solubility of conventional biological resins.

The invention claimed is: 
     
       1. An aliphatic/aromatic copolyester resin composition with hydrolysis resistance and biodegradable property, which is produced by
 mixing an acid component mixture composed of 30 mole % to 70 mole % of aliphatic dicarboxylic acid or its anhydride and 30 mole % to 70 mole % of aromatic dicarboxylic acid or its anhydride; 1.1 to 1.5 mole ratio of aliphatic glycol to one mole of the acid component mixture; and 0.001 to 10 parts by weight of unsaturated aliphatic glycol, relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol, 
 esterifying or transesterifying the resulted mixture by adding 0.0001 to 1 parts by weight of catalyst and stabilizer respectively relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol, and 
 polycondensating the obtained reaction products by adding 0.3 to 1.5 parts by weight of polycondensation catalyst and 0.0001 to 0.5 parts by weight of stabilizer respectively relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol, 
 wherein the unsaturated aliphatic glycol is selected from the group consisting of 2-butene-1,4-diol, 2-hexene-1,5-diol, 3-hexene-1,6-diol, 2-hexene-1,6-diol, 2-butene-1,4-dimethyl-1,4-diol and a mixture of at least two of them, and 
 wherein the aliphatic dicarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid and a mixture of at least two of them. 
 
     
     
       2. The aliphatic/aromatic copolyester resin composition according to  claim 1 , wherein the aromatic dicarboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthoic acid and their ester forming derivatives, and a mixture of at least two of them. 
     
     
       3. The aliphatic/aromatic copolyester resin composition according to  claim 1 , wherein the aliphatic glycol is selected from the group consisting of ethyleneglycol, 1,2-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol and a mixture of at least two of them. 
     
     
       4. The aliphatic/aromatic copolyester resin composition according to  claim 1 , wherein, on esterification or transesterification, a multifunctional compound selected from the group consisting of malic acid, citric acid, trimesic acid, tartaric acid and a mixture of at least two of them is further added in amount of 2 mole % or less based on 100 mole % of the acid component mixture. 
     
     
       5. The aliphatic/aromatic copolyester resin composition according to  claim 1 , wherein, on esterification or transesterification, a multifunctional compound selected from the group consisting of glycerol, pentaerytritol and a mixture of at least two of them is further added in amount of 2 mole % or less based on 100 mole % of the glycol component. 
     
     
       6. The aliphatic/aromatic copolyester resin composition according to  claim 1 , wherein, on esterification or transesterification, an oxazoline compound selected from the group consisting of 2,2-bis-(2-oxazoline), N,N′-hexamethylene-bis-(2-carbamoyl-2-oxazoline), 2,2′-methylene-bis-(2-oxazoline), 2,2′-ethylene-bis-(2-oxazoline), 2,2′-propylene-bis-(2-oxazoline), 1,3-phenylene-bis-(2-oxazoline), 2,2-p-phenylene-bis-(2-oxazoline) and a mixture of at least two of them is further added in amount of 10 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       7. The aliphatic/aromatic copolyester resin composition according to  claim 1 , wherein, on esterification or transesterification, a carbodiimide compound selected from the group consisting of 1,3-dicyclohexylcarbodiimide, bis-(2,6-diisopropyl-phenylene-2,4-carbodiimide), poly-(1,3,5-triisopropyl-phenylene-2,4-carbodiimide) and a mixture of at least two of them is further added in amount of 10 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       8. The aliphatic/aromatic copolyester resin composition according to  claim 1 , wherein, on esterification or transesterification, an isocyanate based compound selected from the group consisting of 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethanediisocyanate and a mixture of at least two of them is further added as a chain extender in amount of 5 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       9. The aliphatic/aromatic copolyester resin composition according to  claim 1 , wherein the composition has a number-average molecular weight of from 30,000 to 60,000 and the weight-average molecular weight of from 50,000 to 300,000, and a melting point of from 80 to 150° C. 
     
     
       10. An injection or extrusion molded article comprising the aliphatic/aromatic copolyester resin composition according to  claim 1 . 
     
     
       11. A compounded composition prepared by adding starch, calcium carbonate or talc to the aliphatic/aromatic copolyester resin composition according to  claim 1 . 
     
     
       12. The aliphatic/aromatic copolyester resin composition according to  claim 2 , wherein, on esterification or transesterification, an isocyanate based compound selected from the group consisting of 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethanediisocyanate and a mixture of at least two of them is further added as a chain extender in amount of 5 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       13. The aliphatic/aromatic copolyester resin composition according to  claim 2 , wherein the composition has a number-average molecular weight of from 30,000 to 60,000 and the weight-average molecular weight of from 50,000 to 300,000, and a melting point of from 80 to 150° C. 
     
     
       14. The aliphatic/aromatic copolyester resin composition according to  claim 3 , wherein, on esterification or transesterification, an isocyanate based compound selected from the group consisting of 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethanediisocyanate and a mixture of at least two of them is further added as a chain extender in amount of 5 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       15. The aliphatic/aromatic copolyester resin composition according to  claim 3 , wherein the composition has a number-average molecular weight of from 30,000 to 60,000 and the weight-average molecular weight of from 50,000 to 300,000, and a melting point of from 80 to 150° C. 
     
     
       16. The aliphatic/aromatic copolyester resin composition according to  claim 4 , wherein, on esterification or transesterification, an oxazoline compound selected from the group consisting of 2,2-bis-(2-oxazoline), N, N′-hexamethylene-bis-(2-carbamoyl-2-oxazoline), 2,2′-methylene-bis-(2-oxazoline), 2,2′-ethylene-bis-(2-oxazoline), 2,2′-propylene-bis-(2-oxazoline), 1,3-phenylene-bis-(2-oxazoline), 2,2-p-phenylene-bis-(2-oxazoline) and a mixture of at least two of them is further added in amount of 10 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       17. The aliphatic/aromatic copolyester resin composition according to  claim 16 , wherein, on esterification or transesterification, an isocyanate based compound selected from the group consisting of 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethanediisocyanate and a mixture of at least two of them is further added as a chain extender in amount of 5 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       18. The aliphatic/aromatic copolyester resin composition according to  claim 16 , wherein the composition has a number-average molecular weight of from 30,000 to 60,000 and the weight-average molecular weight of from 50,000 to 300,000, and a melting point of from 80 to 150° C. 
     
     
       19. The aliphatic/aromatic copolyester resin composition according to  claim 4 , wherein, on esterification or transesterification, an isocyanate based compound selected from the group consisting of 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethanediisocyanate and a mixture of at least two of them is further added as a chain extender in amount of 5 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       20. The aliphatic/aromatic copolyester resin composition according to  claim 4 , wherein the composition has a number-average molecular weight of from 30,000 to 60,000 and the weight-average molecular weight of from 50,000 to 300,000, and a melting point of from 80 to 150° C. 
     
     
       21. The aliphatic/aromatic copolyester resin composition according to  claim 5 , wherein, on esterification or transesterification, an isocyanate based compound selected from the group consisting of 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethanediisocyanate and a mixture of at least two of them is further added as a chain extender in amount of 5 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       22. The aliphatic/aromatic copolyester resin composition according to  claim 5 , wherein the composition has a number-average molecular weight of from 30,000 to 60,000 and the weight-average molecular weight of from 50,000 to 300,000, and a melting point of from 80 to 150° C. 
     
     
       23. The aliphatic/aromatic copolyester resin composition according to  claim 6 , wherein, on esterification or transesterification, an isocyanate based compound selected from the group consisting of 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethanediisocyanate and a mixture of at least two of them is further added as a chain extender in amount of 5 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       24. The aliphatic/aromatic copolyester resin composition according to  claim 6 , wherein the composition has a number-average molecular weight of from 30,000 to 60,000 and the weight-average molecular weight of from 50,000 to 300,000, and a melting point of from 80 to 150° C. 
     
     
       25. The aliphatic/aromatic copolyester resin composition according to  claim 7 , wherein, on esterification or transesterification, an isocyanate based compound selected from the group consisting of 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethanediisocyanate and a mixture of at least two of them is further added as a chain extender in amount of 5 parts by weight or less relative to a total of 100 parts by weight of the acid component mixture and the aliphatic glycol. 
     
     
       26. The aliphatic/aromatic copolyester resin composition according to  claim 7 , wherein the composition has a number-average molecular weight of from 30,000 to 60,000 and the weight-average molecular weight of from 50,000 to 300,000, and a melting point of from 80 to 150° C.